WO2022241979A1

WO2022241979A1 - Polyamide fiber having anti-ultraviolet performance and preparation method therefor

Info

Publication number: WO2022241979A1
Application number: PCT/CN2021/118382
Authority: WO
Inventors: 吴丹丹; 陈登龙; 刘金玲; 刘志鹏; 林金火; 雷自强
Original assignee: 福建师范大学泉港石化研究院
Priority date: 2021-05-17
Filing date: 2021-09-15
Publication date: 2022-11-24
Also published as: CN113265716B; CN113265716A

Abstract

The present application relates to the technical field of polyamide fiber materials, and in particular, discloses a polyamide fiber having anti-ultraviolet performance and a preparation method therefor. Firstly, triisopropyl borate, 2-amino-3-hydracrylic acid, and dihydric alcohol serve as raw materials to prepare a bifunctional group chelating type borate coupling agent having amino and carboxyl; a nano rare earth oxide is modified by using the synthesized coupling agent; then in-situ polymerization is performed on the modified nano rare earth oxide and caprolactam to prepare a nylon resin containing the nano rare earth oxide; and finally, spinning is performed to prepare the polyamide fiber. The obtained polyamide fiber has more lasting and more stable and excellent anti-ultraviolet performance.

Description

A kind of nylon fiber with anti-ultraviolet performance and preparation method thereof

technical field

The invention belongs to the technical field of nylon fiber materials, and in particular relates to a nylon fiber with anti-ultraviolet performance and a preparation method thereof.

Background technique

Since the 20th century, with the acceleration of modern industrial processes, exhaust gas emissions and the use of various fluorides, the ozone layer has been damaged to a certain extent, and the ultraviolet radiation reaching the ground has gradually increased, resulting in increasingly serious harm. In the face of increasingly serious environmental problems, people pay more attention to their own protection in addition to the protection of the environment. Anti-ultraviolet textiles, like other protective products, have received people's attention. At present, the research and development of anti-ultraviolet functional fabrics is being carried out internationally, and anti-ultraviolet finishing has become a new and very promising development direction.

Nylon is one of the earliest industrially produced chemical fiber varieties in the world. It has excellent properties such as wear resistance and corrosion resistance. The fabric made of nylon is light, soft, and gentle to the skin. It is widely used in high-end clothing and special functional clothing. However, the main disadvantage of nylon fiber is that it has poor light resistance and heat resistance, and it is prone to yellowing and strength reduction under long-term ultraviolet light irradiation, which affects the usability. Therefore, the research and development of UV-resistant functional nylon fabric is a topic with important practical significance and economic value.

At present, the commonly used method to improve the UV resistance of nylon fiber is to add organic UV absorbers or UV shielding agents. The mechanism of organic ultraviolet absorbers is to capture or quench the active free radicals generated by high-energy ultraviolet rays breaking polymer molecular chains, but organic ultraviolet absorbers are all small molecular weight organic compounds, whether it is the absorption of ultraviolet light or the The capture of free radicals has certain limitations, and with the prolongation of use time, migration and degradation will occur, resulting in a gradual decline in the UV resistance of the material and eventually failure. However, ultraviolet shielding agents such as ZnO have problems such as high photocatalytic activity and insufficient short-wavelength absorption capacity due to ZnO.

In addition, there is also the prior art of applying nanoparticles with anti-ultraviolet function to nylon fibers, but such nanoparticles are small and have a large specific surface area, and are prone to agglomeration in nylon fibers. The general way to solve the agglomeration is to add conventional surfactants. The principle of these surfactants to solve the agglomeration is to eliminate the surface charge of the nanoparticles and enhance the lipophilicity of the nanoparticles, so that the nanoparticles can be doped into the nylon fiber. However, the stability of this method of combining nanoparticles with nylon fibers is still not good enough, which greatly reduces the anti-ultraviolet performance of the nylon fibers; to the color of the material itself.

Therefore, finding a substance or method that can combine anti-ultraviolet functional nanoparticles with nylon fibers more stably and uniformly, and finding a more suitable anti-ultraviolet functional nano-particles for nylon fibers have become urgent problems to be solved.

technical problem

How to solve the chemical bond combination of nano-rare earth oxide and nylon resin, so as to improve the anti-ultraviolet function of nylon fiber.

technical solution

The purpose of the present invention is to provide a nylon fiber with anti-ultraviolet performance, which has more durable, stable and excellent anti-ultraviolet performance.

The above-mentioned purpose of the present invention is achieved by the following technical scheme: a kind of nylon fiber with anti-ultraviolet performance is prepared from triisopropyl borate, 2-amino-3-hydroxypropionic acid, glycol and catalyst as raw materials with Amino and carboxyl bifunctional chelating borate coupling agents, and use it to modify the surface of nano-rare earth oxides, and in-situ polymerize the modified nano-rare earth oxides with caprolactam and process to obtain the The nylon fiber with anti-ultraviolet performance is described.

Further, the molar ratio of triisopropyl borate, glycol, and 2-amino-3-hydroxypropionic acid is 1; 1-1.05: 1-1.05.

Further, the dihydric alcohol is one of ethylene glycol, propylene glycol and butanediol.

Further, the mass ratio of the nano rare earth oxide to the bifunctional chelating borate coupling agent is 100:0.1-5.

Further, the nano rare earth oxide is one or both of nano rare earth cerium oxide and nano rare earth lanthanum oxide.

Further, the mass ratio of the nano rare earth oxide to the caprolactam is 0.1-5:100.

Using the above technical scheme, the 4f electrons of nano-rare earth oxides have no absorption for visible light, but show excellent absorption capacity for ultraviolet rays. The combination of nano-rare earth oxides and nylon fibers not only makes the finally obtained nylon fibers have good UV resistance, but also And it will not affect the original color of nylon fiber.

Using the interaction between triisopropyl borate, 2-amino-3-hydroxypropionic acid and diols, a bifunctional chelating borate coupling agent with amino and carboxyl groups was synthesized, and it was used for nano The surface of the rare earth oxide is modified and modified. The modified rare earth oxide surface has functional functional groups that can react with caprolactam, so that the nano-sized rare earth oxide nanoparticles can be firmly locked in the polymer matrix in the form of chemical bonds. Therefore, the ultraviolet resistance performance of the finally obtained nylon fiber is more durable and excellent.

Another object of the present invention is to provide a method for preparing nylon fibers with UV resistance, which has the advantages of convenient and simple operation.

The above object of the present invention is achieved through the following technical solutions: a preparation method of polyamide fibers with anti-ultraviolet properties, prepared according to the following steps:

S1. In a three-necked flask with a thermometer, a stirrer, and a reflux condenser, add triisopropyl borate and a catalyst, then raise the temperature to 80-130°C, and add glycol dropwise under constant stirring, and heat to reflux for 60- After 120 minutes, add the measured amount of 2-amino-3-hydroxypropionic acid, continue the reflux reaction at 130-180°C for 90-150 minutes, and distill the isopropanol under reduced pressure to obtain the bifunctional group chelating borate coupling agent;

S2. Dry the nano-rare earth oxide at 105°C for 1-4 hours, and then add it and the bifunctional group chelating borate coupling agent prepared in S1 into the high-mixture that has been heated to 115-140°C in proportion. React in the machine for 15-60 minutes, and after cooling, the modified nano-rare earth oxide can be obtained;

S3. Mix the modified nano-rare earth oxide, caprolactam, and water in proportion, put them into a polymerization kettle, heat to 250°C-270°C, and undergo a hydrolysis polymerization reaction for 10-24 hours to obtain a compound with anti-ultraviolet properties. Nylon 6 resin is obtained through continuous extrusion, pelletizing, continuous extraction, and continuous nitrogen drying to obtain nylon 6 chips with anti-ultraviolet properties, and spinning to obtain the nylon fibers with anti-ultraviolet properties.

Further, the catalyst is one or both of sodium methoxide, sodium ethoxide, sodium isopropoxide, sodium tert-butoxide, potassium methoxide, potassium ethoxide, potassium isopropoxide, and potassium tert-butoxide.

Further, the mass ratio of caprolactam to water is 100:2.

Beneficial effect

The present invention has the following beneficial effects:

1. The synthesized bifunctional chelating borate coupling agent can effectively solve the problem of agglomeration of nano-rare earth oxides, and combine nano-rare earth oxides and PA6 matrix with chemical bonds, so that the finally obtained nylon fiber has UV resistance More durable and excellent performance;

2. Choose the combination of nano-rare earth oxides and nylon fibers. Nano-rare earth oxides not only have excellent characteristics such as non-toxicity, stability, and non-migration, but also have good ultraviolet shielding ability. A small amount of addition will not affect the original color of the fiber.

The synthesized bifunctional chelating borate coupling agent has a chelating group, so the coupling agent has good hydrolysis resistance, can avoid the influence of moisture on the reaction system, and ensure the stability of the reaction process.

BEST MODE FOR CARRYING OUT THE INVENTION

A kind of nylon fiber with anti-ultraviolet performance is prepared according to the following steps:

S1. Add 0.50 mol triisopropyl borate and 0.28 g sodium isopropoxide to a three-necked flask with a thermometer, a stirrer, and a reflux condenser, then raise the temperature to 100°C, and add 0.52 mol ethyl alcohol dropwise under constant stirring. Diol, heated and refluxed for 90 minutes, then added 0.51mol of 2-amino-3-hydroxypropionic acid, continued to reflux for 120 minutes at 150°C, and distilled off isopropanol under reduced pressure to obtain a chelating compound containing two functional groups. type borate coupling agent.

S2. Dry the nano-rare earth cerium oxide at 105°C for 2 hours, and then add it and the borate coupling agent prepared above in a mass ratio of 100:1 to the high mixer that has been heated to 120°C for 45 Minutes, after cooling, borate-modified nano rare earth cerium oxide is obtained.

S3. Mix the modified nano-rare earth cerium oxide, caprolactam, and water at a mass ratio of 2:100:2, put them into a polymerization kettle, heat to 250° C., and undergo hydrolysis polymerization for 14 hours to obtain the described Nano-rare earth cerium oxide modified nylon 6 resin with anti-ultraviolet properties, and then the polymer melt is continuously extruded, pelletized, continuously extracted, and dried in nitrogen to obtain nylon 6 chips for anti-ultraviolet fibers. Put the chips into a bidirectional screw extruder, and prepare nylon 6 fibers through melting, spinning, cooling, drawing, winding and shaping.

Embodiments of the present invention

The present invention is described in further detail below in conjunction with embodiment.

Neither the endpoints nor any values of the ranges disclosed herein are limited to that precise range or value, and these ranges or values are understood to include values close to these ranges. For numerical ranges, between the endpoints of each range, between the endpoints of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, these values Ranges should be considered as specifically disclosed herein.

Embodiment 1: A kind of nylon fiber with anti-ultraviolet performance is prepared according to the following steps:

S1. Add 0.50 mol triisopropyl borate and 0.28 g sodium isopropoxide to a three-necked flask with a thermometer, a stirrer, and a reflux condenser, then raise the temperature to 100°C, and add 0.51 mol ethyl alcohol dropwise under constant stirring. Diol, heated and refluxed for 90 minutes, then added 0.51mol of 2-amino-3-hydroxypropionic acid, continued to reflux for 120 minutes at 150°C, and distilled off isopropanol under reduced pressure to obtain a chelating compound containing two functional groups. type borate coupling agent.

S2. Dry the nano-rare earth cerium oxide at 105°C for 2 hours, then add it and the borate coupling agent prepared above in a mass ratio of 100:1 to the high mixer that has been heated to 120°C for 30 minutes. Minutes, after cooling, borate-modified nano rare earth cerium oxide is obtained.

S3. Mix the modified nano-rare earth cerium oxide, caprolactam, and water in a mass ratio of 0.3:100:2, put them into a polymerization kettle, heat to 250° C., and undergo hydrolysis polymerization for 14 hours to obtain the described Nano-rare earth cerium oxide modified nylon 6 resin with anti-ultraviolet properties, and then the polymer melt is continuously extruded, pelletized, continuously extracted, and dried in nitrogen to obtain nylon 6 chips for anti-ultraviolet fibers. Put the chips into a bidirectional screw extruder, and prepare nylon 6 fibers through melting, spinning, cooling, drawing, winding and shaping.

Embodiment 2: A kind of nylon fiber with anti-ultraviolet performance is prepared according to the following steps:

S1. Add 0.50 mol triisopropyl borate and 0.28 g sodium isopropoxide to a three-necked flask with a thermometer, a stirrer, and a reflux condenser, then raise the temperature to 100°C, and add 0.52 mol ethyl alcohol dropwise under constant stirring. Diol, heated to reflux for 90 minutes, then added 0.52mol of 2-amino-3-hydroxypropionic acid, continued the reflux reaction at 150°C for 120 minutes, and distilled off isopropanol under reduced pressure to obtain a chelating compound containing bifunctional groups. type borate coupling agent.

S3. Mix the modified nano-rare earth cerium oxide, caprolactam, and water in a mass ratio of 0.5:100:2, put them into a polymerization kettle, heat to 250°C, and undergo hydrolysis polymerization for 14 hours to obtain the described Nano-rare earth cerium oxide modified nylon 6 resin with anti-ultraviolet properties, and then the polymer melt is continuously extruded, pelletized, continuously extracted, and dried in nitrogen to obtain nylon 6 chips for anti-ultraviolet fibers. Put the chips into a bidirectional screw extruder, and prepare nylon 6 fibers through melting, spinning, cooling, drawing, winding and shaping.

Embodiment three: a kind of polyamide fiber with anti-ultraviolet performance is prepared according to the following steps:

S1. Add 0.50mol triisopropyl borate and 0.28g sodium ethylate to a three-neck flask with thermometer, stirrer, and reflux condenser, then raise the temperature to 100°C, and add 0.52mol ethylene glycol dropwise under constant stirring , heated to reflux for 90 minutes, then added 0.51mol of 2-amino-3-hydroxypropionic acid, continued the reflux reaction at 150°C for 120 minutes, and distilled off isopropanol under reduced pressure to obtain chelated boron with bifunctional groups Ester coupling agent.

S3. Mix the modified nano-rare earth cerium oxide, caprolactam, and water in a mass ratio of 0.7:100:2, put them into a polymerization kettle, heat to 250°C, and undergo hydrolysis polymerization for 14 hours to obtain the described Nano-rare earth cerium oxide modified nylon 6 resin with anti-ultraviolet properties, and then the polymer melt is continuously extruded, pelletized, continuously extracted, and dried in nitrogen to obtain nylon 6 chips for anti-ultraviolet fibers. Put the chips into a bidirectional screw extruder, and prepare nylon 6 fibers through melting, spinning, cooling, drawing, winding and shaping.

Embodiment 4: A kind of nylon fiber with anti-ultraviolet performance is prepared according to the following steps:

S3. Mix the modified nano-rare earth cerium oxide, caprolactam, and water at a mass ratio of 1:100:2, put them into a polymerization kettle, heat to 250° C., and undergo hydrolysis polymerization for 14 hours to obtain the described Nano-rare earth cerium oxide modified nylon 6 resin with anti-ultraviolet properties, and then the polymer melt is continuously extruded, pelletized, continuously extracted, and dried in nitrogen to obtain nylon 6 chips for anti-ultraviolet fibers. Put the chips into a bidirectional screw extruder, and prepare nylon 6 fibers through melting, spinning, cooling, drawing, winding and shaping.

Embodiment five: a kind of polyamide fiber with anti-ultraviolet performance is prepared according to the following steps:

Embodiment 6: A kind of nylon fiber with anti-ultraviolet performance is prepared according to the following steps:

S1. Add 0.50 mol triisopropyl borate and 0.28 g potassium isopropoxide to a three-necked flask with a thermometer, a stirrer, and a reflux condenser, then raise the temperature to 100°C, and add 0.52 mol ethyl borate dropwise under continuous stirring. Diol, heated and refluxed for 90 minutes, then added 0.51mol of 2-amino-3-hydroxypropionic acid, continued to reflux for 120 minutes at 150°C, and distilled off isopropanol under reduced pressure to obtain a chelating compound containing two functional groups. type borate coupling agent.

S3. Mix the modified nano-rare earth cerium oxide, caprolactam, and water in a mass ratio of 4:100:2, put them into a polymerization kettle, heat to 250° C., and undergo hydrolysis polymerization for 14 hours to obtain the described Nano-rare earth cerium oxide modified nylon 6 resin with anti-ultraviolet properties, and then the polymer melt is continuously extruded, pelletized, continuously extracted, and dried in nitrogen to obtain nylon 6 chips for anti-ultraviolet fibers. Put the chips into a bidirectional screw extruder, and prepare nylon 6 fibers through melting, spinning, cooling, drawing, winding and shaping.

Embodiment 7: A kind of nylon fiber with anti-ultraviolet performance is prepared according to the following steps:

S2. Dry the nano-rare earth lanthanum oxide at 105°C for 2 hours, then add it and the borate coupling agent prepared above in a mass ratio of 100:1 to the high mixer that has been heated to 120°C for 45 Minutes, after cooling, borate-modified nano rare earth lanthanum oxide is obtained.

S3. Mix the modified nano-rare earth lanthanum oxide, caprolactam, and water at a mass ratio of 1:100:2, put them into a polymerization kettle, heat to 250°C, and undergo hydrolysis polymerization for 14 hours to obtain the described Nylon 6 resin for fibers with anti-ultraviolet properties modified by nano-rare earth lanthanum oxide, and then the polymer melt is continuously extruded, pelletized, extracted continuously, and dried in nitrogen to obtain nylon 6 chips for anti-ultraviolet fibers. Put the chips into a bidirectional screw extruder, and prepare nylon 6 fibers through melting, spinning, cooling, drawing, winding and shaping.

Comparative example 1: Mix unmodified nano-rare earth cerium oxide, caprolactam, and water in a mass ratio of 2:100:2, put them into a polymerization kettle, heat to 250°C, and undergo hydrolysis polymerization for 14 hours to obtain Said nano rare earth cerium oxide modified nylon 6 resin with anti-ultraviolet properties, and then the polymer melt is continuously extruded, pelletized, continuously extracted, and continuously dried with nitrogen to obtain nylon 6 chips for anti-ultraviolet fibers. Put the chips into a bidirectional screw extruder, and prepare nylon 6 fibers through melting, spinning, cooling, drawing, winding and shaping.

Comparative example 2: Mix nano-rare earth cerium oxide, caprolactam, and water modified with fatty alcohol polyoxyethylene ether (AEO-9) at a mass ratio of 2:100:2, put them into a polymerization kettle, and heat to After 14 hours of hydrolysis and polymerization at 250°C, the nano-rare earth cerium oxide-modified nylon 6 resin with anti-ultraviolet properties was obtained, and then the polymer melt was continuously extruded, pelletized, continuously extracted, and nitrogen was continuously extracted. After drying, nylon 6 slices were obtained for anti-ultraviolet fibers. Put the chips into a bidirectional screw extruder, and prepare nylon 6 fibers through melting, spinning, cooling, drawing, winding and shaping.

Comparative Example 3: Mix caprolactam and water at a mass ratio of 100:2, put them into a polymerization kettle, heat to 250°C, and undergo hydrolysis and polymerization for 14 hours to obtain the nano-rare earth cerium oxide modified Nylon 6 resin is used for anti-ultraviolet fibers, and then the polymer melt is continuously extruded, pelletized, continuously extracted, and continuously dried with nitrogen to obtain nylon 6 chips for anti-ultraviolet fibers. Put the chips into a bidirectional screw extruder, and prepare nylon 6 fibers through melting, spinning, cooling, drawing, winding and shaping.

Performance tests were performed on the samples obtained in Examples 1 to 7, Comparative Example 1, Comparative Example 2 and Comparative Example 3, and Table 1 was obtained.

Table 1 Performance test results

Comparing Examples 1 to 7 with Comparative Example 3, it is found that the addition of nanometer rare earth oxides can effectively improve the UV resistance of nylon fibers.

Compared with Example 5 and Comparative Example 1, the fiber strength and UPF of Comparative Example 1 all decreased, because Comparative Example 1 did not utilize the chelating type borate coupling agent containing bifunctional groups to oxidize nano-rare earth Cerium is more uniformly and stably combined with the PA6 matrix, resulting in poor stability and dispersion of nano-rare earth cerium oxide in PA6, resulting in poor UV resistance and a significant decline in the mechanical properties of the fiber.

Compare with implementation five and comparative example two, the fiber strength of comparative example two and UPF all decline to some extent, this is because comparative example two has only adopted common surfactant to modify nano-rare earth cerium oxide, this modification The only way is to eliminate the high surface charge of nano-rare-earth cerium oxide and improve its lipophilicity. The modified nano-rare-earth cerium oxide obtained in this way will not undergo copolymerization reaction with caprolactam. Therefore, the stability and dispersion of the combination of nano-rare earth cerium oxide and PA6 matrix are compromised, so that the anti-ultraviolet performance of Comparative Example 2 is not good enough.

The preferred embodiments of the present invention have been described in detail above, however, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the disclosed content of the present invention. All belong to the protection scope of the present invention.

Claims

A nylon fiber with anti-ultraviolet properties, characterized in that, using triisopropyl borate, 2-amino-3-hydroxypropionic acid and glycol as raw materials to prepare bifunctional group chelated boron with amino and carboxyl groups ester coupling agent, and then use the synthesized coupling agent to modify the nano-rare earth oxide, and then in-situ polymerize the modified nano-rare earth oxide and caprolactam and process to obtain the UV-resistant Nylon fiber.
A kind of nylon fiber with anti-ultraviolet performance according to claim 1, characterized in that the molar ratio of triisopropyl borate, glycol, and 2-amino-3-hydroxypropionic acid is 1:1 -1.05: 1-1.05.
A kind of nylon fiber with anti-ultraviolet performance according to claim 1, is characterized in that, described glycol is the one in ethylene glycol, propylene glycol, butanediol.
A kind of nylon fiber with anti-ultraviolet performance according to claim 1, characterized in that, the mass ratio of the nano rare earth oxide to the bifunctional group chelating borate coupling agent is 100:0.1- 5.
A kind of nylon fiber with anti-ultraviolet performance according to claim 1, characterized in that, the nano rare earth oxide is one or both of nano rare earth cerium oxide and nano rare earth lanthanum oxide.
The nylon fiber with UV resistance according to claim 1, characterized in that the mass ratio of the nano rare earth oxide to the caprolactam is 0.1-5:100.
A kind of preparation method of the nylon fiber with anti-ultraviolet performance according to claim 1, is characterized in that, prepares according to the following steps:

S1. In a three-necked flask with a thermometer, a stirrer, and a reflux condenser, add triisopropyl borate and a catalyst, then raise the temperature to 80-130°C, and add glycol dropwise under constant stirring, and heat to reflux for 60- After 120 minutes, add the measured amount of 2-amino-3-hydroxypropionic acid, continue the reflux reaction at 130-180°C for 90-150 minutes, and distill the isopropanol under reduced pressure to obtain the bifunctional group chelating borate coupling agent;

S2. Dry the nano-rare earth oxide at 105°C for 1-4 hours, and then add it and the bifunctional group chelating borate coupling agent prepared in S1 into the high-mixture that has been heated to 115-140°C in proportion. React in the machine for 15-60 minutes, and after cooling, the modified nano-rare earth oxide can be obtained;

S3. Mix the modified nano-rare earth oxide, caprolactam, and water in proportion, put them into a polymerization kettle, heat to 250°C-270°C, and undergo hydrolysis polymerization for 10-24 hours to obtain UV-resistant Nylon 6 resin is then continuously extruded, pelletized, continuously extracted, and continuously dried with nitrogen to obtain nylon 6 chips with anti-ultraviolet properties, and the nylon fibers with anti-ultraviolet properties are obtained through spinning.
A kind of preparation method of nylon fiber with anti-ultraviolet performance according to claim 7, is characterized in that, described catalyst is sodium methylate, sodium ethylate, sodium isopropoxide, sodium tert-butoxide, potassium methylate, potassium ethylate , Potassium isopropoxide, Potassium tert-butoxide or both.
A method for preparing nylon fibers with anti-ultraviolet properties according to claim 7, characterized in that the mass ratio of caprolactam to water is 100:2.